WO2002044299A1 - Composition de materiau d'etancheite pouvant durcir par apport d'energie - Google Patents

Composition de materiau d'etancheite pouvant durcir par apport d'energie Download PDF

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Publication number
WO2002044299A1
WO2002044299A1 PCT/JP2001/010529 JP0110529W WO0244299A1 WO 2002044299 A1 WO2002044299 A1 WO 2002044299A1 JP 0110529 W JP0110529 W JP 0110529W WO 0244299 A1 WO0244299 A1 WO 0244299A1
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WIPO (PCT)
Prior art keywords
component
styrene
meth
weight
composition according
Prior art date
Application number
PCT/JP2001/010529
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English (en)
Japanese (ja)
Inventor
Yuichi Nishida
Takanori Sugiki
Kazuhiko Yoshizumi
Yoshio Kishimoto
Original Assignee
Nichiban Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nichiban Company Limited filed Critical Nichiban Company Limited
Priority to JP2002546649A priority Critical patent/JP4184788B2/ja
Priority to US10/433,237 priority patent/US6818256B2/en
Priority to EP01998609A priority patent/EP1348750A4/fr
Priority to KR1020037007293A priority patent/KR100820462B1/ko
Publication of WO2002044299A1 publication Critical patent/WO2002044299A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0243—Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0247—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof

Definitions

  • the present invention relates to an oil-surface adhesive energy-curable sealant composition having sufficient adhesiveness to an oil-surface steel plate.
  • the present invention relates to an energy-curable sealing agent composition such as light and heat which has a low odor during production, application and curing of a product, has good adhesion to various oil-based materials after curing, and has excellent low-temperature flexibility.
  • sealing agents are used in large quantities in the automobile body manufacturing process for protection against corrosion and corrosion.
  • the body of an automobile is usually press-formed from cold-rolled steel sheet, zinc plated steel sheet, aluminum alloy, etc. to which press oil or fire-proof oil has adhered, then subjected to a degreasing (oil washing) process, electrodeposition coating, and a sealing agent. Apply and dry, apply middle coat and top coat. In some cases, a sealing agent may be applied and dried before the degreasing step.
  • press oil and fire-proof oil are removed by washing. I had to. This requires washing water and chemicals (additives such as surfactants), and requires a drying step and a wastewater treatment step.
  • Sealing agents used to protect automobiles from corrosion include PVC-based and urethane-based sealants, but most of them are PVC-based, which are plasticizers and stabilizers for polyvinyl chloride. Is impregnated.
  • PVC sealers have a problem that they cannot be easily incinerated at the time of disposal because they contain chlorine.
  • the urethane type is a two-component type or a moisture-curing type, and has drawbacks such as the necessity of mixing by a mixing device before construction and the long time required for setting.
  • these sealants are used for cold-pressed steel sheets, Poor adhesion to plated steel sheets and aluminum alloys may cause runoff in the oil cleaning process before the painting process.
  • the present inventors have already disclosed in the specification of Japanese Patent Application No. 11-223398 a solution of an acrylate monomer having a solubility parameter (SP value) of 9 to 14 as a means for solving these problems.
  • SP value solubility parameter
  • a filler such as hydrophobic silica and a phosphate ester monomer
  • a photocurable sealant composition having excellent oil-surface adhesion is proposed.
  • the acrylate as a main component proposed by the present inventors is specifically, 2-hydroxy-13-phenoxypropyl acrylate or 2-acryloyloxicetyl 2-. It is hydroxyethyl phthalic acid or phenoxysethyl acrylate.
  • the present invention (1) to (9) provide a light-curing sealing agent composition which has a low odor during production, application and curing of a product, has good adhesion to various oily surface materials after curing, and has excellent low-temperature flexibility. It is intended to
  • the present inventions (10) to (11) have low odor during production, application and curing of a product, have good adhesion to various oil surface materials after curing, have excellent low-temperature flexibility, and have an electrodeposition coating process. It is an object of the present invention to provide a light / thermosetting sealing agent composition which does not generate air bubbles at the same time.
  • examples of the photocurable sealant composition having excellent oil surface adhesiveness and eliminating the need for a washing step include (meth) acrylate monomers having a solubility parameter of 9 to 14 as described above, hydrophobic silica, and the like. Contains filler, phosphate ester monomer, etc. Things have been suggested. In this proposal, hydrophobic silica was included as an essential component to the monomer component, but the objectives were viscosity, workability (no stringing, no dripping) as oil-absorbing and sealing agent properties. This was to satisfy the hardness after curing. However, oil surface adhesion is required not only in the field of sealants, but also in the field of coatings. Then, an object of the present invention (13) to (15) is to provide a composition having not only a high viscosity such as a sealing agent but also a low viscosity. Disclosure of the invention
  • the inventors of the present invention have shown low-temperature flexibility after hardening while maintaining oil-surface adhesion to various steel sheets, and have also conducted various studies to reduce smoke and odor during product manufacturing and ultraviolet irradiation. As a result, they found that these problems could be solved by using a specific monomer, and completed the present invention. Furthermore, they have found that the addition of a thermoplastic resin can further improve the adhesiveness, and can also reduce smoke and odor during ultraviolet irradiation.
  • the present invention (1) provides an energy-curable silicone containing (a) a (meth) acrylate monomer having a phenyl group having a molecular weight of 200 or more and (b) a photoreaction initiator. It is a ring agent composition.
  • the component (a) is represented by the formula:
  • X and Y each independently represent ⁇ or CH 3 ; ⁇ represents an integer of 2 to 10; Ph represents a phenyl group; R is C a H 2ffl Represents +1 ; m is 0 to
  • the compound of the above invention (1) which is a compound represented by the following formula:
  • the present invention (3) further comprises (a) ′ a (meth) acrylate ester containing a phosphate group or a salt thereof, and / or a (meth) acrylate ester containing a sulfonic group or a salt thereof, and And / or a composition according to the invention (1) or (2), which contains an acrylic acid ester containing a carboxyl group or a salt thereof.
  • the composition according to any one of the inventions (1) to (3), which is an acetophenone or an acetylsulfonoxide compound. is there.
  • the invention (5) is the composition according to any one of the inventions (1) to (4), further comprising (c) a thermoplastic resin.
  • the component (c) is preferably composed of an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, a styrene-butadiene-styrene block copolymer, a styrene-ethylenebutylene copolymer.
  • the composition according to the invention (5) which is a styrene block copolymer, a styrene-ethylene-propylene-styrene-block copolymer, or a styrene-1,4-butadiene-butylene-styrene block copolymer, or polystyrene.
  • the present invention (7) is the composition according to any one of the inventions (1) to (6), further comprising (d) a filler.
  • the invention (8) is the composition according to the invention (7), wherein the component (d) is silica or silica subjected to hydrophobic treatment.
  • the present invention (9) relates to an acrylic acid ester containing a phosphoric acid group or a salt thereof with respect to 100 parts by weight of a (meth) acrylate monomer having a phenyl group having a molecular weight of 200 or more; / Or containing sulfonic acid groups or salts thereof (medium) including acrylates and Z or carboxyl groups or salts thereof
  • An energy-curable resin containing 0 to 100 parts by weight of a (meth) acrylate, 0 to 60 parts by weight of a hydrophobized silica, 0 to 50 parts by weight of a thermoplastic resin, and 0.01 to 20 parts by weight of a photoinitiator.
  • One is a ring agent composition.
  • the present inventors have shown the adhesion to various materials and low-temperature flexibility after hardening while maintaining the oil surface fixability to various steel sheets, and also energizing the adherend for electrodeposition coating. Even after diligent efforts were made to prevent foaming, an epoxy resin curing system was introduced into the system of the inventions (1) to (9), and a polymer alone was used without containing a phenyl group. We have found that these problems can be solved by using together a (meth) acrylate monomer having a glass transition point of less than 20 ° C when cured.
  • the present invention (10) further comprises (a) '' a (meth) acrylate monomer not having a phenyl group having a glass transition point of not more than 120 ° C. at the time of homopolymerization, and (e) The invention according to the above (1), comprising an epoxy resin and (f) a latent curing agent.
  • the present invention (11) is characterized in that component (a) + component (a) '' 100 parts by weight (when component (c) is present, component (a) + component (a) '' + component (c (10)
  • component (a) + component (a) '' + component (c) The composition according to the above (10), wherein the composition contains 20 to 200 parts by weight of the component (e) and the component (f) with respect to 100 parts by weight.
  • the present invention (12) is the composition according to any one of the above inventions (1) to (11), which is oily surface adhesive.
  • the present inventors have found that when a copolymer having polystyrene or styrene as a copolymer component is used, oil-surface adhesion is exhibited without using hydrophobic silica, and a composition having a low viscosity is also obtained. And found that the present invention was completed.
  • the present invention (13) provides (1) a (meth) acrylate monomer having a phenyl group having a solubility parameter of 9 to 14; and (2) a copolymer having polystyrene or styrene as a copolymer component. And (3) an energy-curable oil-side adhesive composition containing a photoreaction initiator.
  • the component (2) may be a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer, a styrene-ethylene
  • the present invention further comprises (3) a (meth) acrylate monomer containing at least one group selected from a phosphate group, a sulfonic acid group, a carboxyl group and salts thereof.
  • a (meth) acrylate monomer containing at least one group selected from a phosphate group, a sulfonic acid group, a carboxyl group and salts thereof.
  • Component (a) is not particularly limited as long as it is a (meth) acrylate monomer having a phenyl group having a molecular weight of 200 or more.
  • a (meth) acrylate monomer having a phenyl group having a molecular weight of 200 or more for example, the formula: CH 2 CXCOO (CH 2 CH (Y) O) n -P h R
  • X and Y each independently represent ⁇ or CH 3 ; ⁇ represents an integer of 2 to 10; Ph represents a phenyl group; R represents CE H represents 2aH ; m represents an integer of 0 to 12).
  • Specific examples include phenoxypolyethylene glycol acrylate, phenoxypolypropylene glycol acrylate, nonylphenol ethanoloxide-modified acrylate, and the like.
  • n is preferably 2 to 4 and R is H.
  • Such (meth) acrylic acid esters are commercially available.
  • the photoreaction initiator of the component (b) and the component (3) is not particularly limited, and a general-purpose photoinitiator can be used.
  • a general-purpose photoinitiator can be used.
  • organic peroxides benzoin compounds, acetophenones, benzophenones, thioxanthones, peroxyloxime esters, phenyldalioxylates, benzyls, azo compounds, diphenyldisulphide compounds And phosphyl phosphoxide compounds, organic dye compounds, iron-phthalocyanine compounds, and the like.
  • Particularly preferred are benzoin compounds, acetophenones, phenyldalioxylates, and phosphyl phosphoxide compounds. . These may be used in combination.
  • the (meth) acrylic acid ester having an acidic group of the component (a) ′ is a component for improving the adhesiveness to a metal, for example, a (meth) acrylic acid ester containing a phosphate group or a salt thereof, For example, 2- (meth) acryloyloxyshethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, salts thereof; (meth) acrylic acid esters containing a lipoxyl group or a salt thereof, For example, 2- (meth) acryloyl mouth xicetyl phthalic acid, 2_ (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyl mouth xicetyl hexahydrophthalic acid, salts thereof; (meth) acrylic esters containing sulfonic acid groups or salts thereof For example, 2-acrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methyl
  • Such (meth) acrylic acid esters are commercially available.
  • 2-methacryloyloxyshethyl acid phosphate Kyoeisha Chemical Co., Ltd. has a trade name of Light Acrylate P-1M.
  • 2-acrylic acid xishethylphthalic acid can be obtained from Kyoeisha Chemical Co., Ltd. under the trade name Liteacrylate H0A-MPL.
  • the thermoplastic resin as the component (c) is preferably a resin which disperses and dissolves in the (meth) acrylate monomer which is a main component and which increases the transparency of the entire system before curing.
  • SIS styrene-isoprene-styrene block copolymer
  • SBS styrene-butadiene-styrene block copolymer
  • SEBS styrene-ethylenebutylene-styrene block copolymer
  • styrene-ethylene Styrene block copolymers such as propylene-styrene block copolymer (SEPS), styrene-1,4-butadiene-butylene-styrene copolymer (SBBS), polyurethane-based thermoplastic elastomer, polyester-based thermoplastic Elastomers, polyamide-based thermoplastic elastomers, ethylene-vinyl acetate-based thermo
  • EVA, SBBS and SBS are particularly preferred.
  • EVA Flex 45X, 40Y, 150, 210, etc. (Mitsui / Dupont Polychemical) Asahi Kasei Kogyo Co., Ltd.) and SBS include KRATON D-1101, D-KX155, D-1122X, and D-1184 (all manufactured by Shell Chemical).
  • the filler of the component (d) is not particularly limited, and examples thereof include silica or silica subjected to a hydrophobic treatment.
  • fine powder obtained by hydrophobizing the silica surface with an alkyl group or the like can be used. This is preferable because it has an affinity for oil, has a property of thickening into a paste having a high oil-absorbing ability, and does not inhibit light transmittance.
  • the carbon content is preferably 0.5 to 6% by weight, more preferably 1 to 4% by weight, and the average diameter of the primary particles is preferably 10 Onm or less, more preferably 4% or less. Onm or less.
  • Examples of commercially available products include Aerosil R972, R974, State 0, RY200, Rinse, Gei, R812S ⁇ Nippon Aerosil Co., Ltd. ⁇ and the like.
  • the (meth) acrylate monomer having no phenyl group of the component (a) '' has a glass transition point of not more than 120 ° C at the time of homopolymerization, and has a phenol group in the molecule.
  • a (meth) acrylate monomer that does not contain but those having an ethylene oxide chain of 2 or less and a molecular weight of 200 or more are preferred.
  • the epoxy resin of the component (e) is not particularly limited, but is preferably a liquid one so as not to increase the viscosity.
  • Epikoto 828 Japanese Epoxy Resin Co., Ltd.
  • Epicure DI CY7 Japanese Epoxy Resin Co., Ltd.
  • the latent curing agent of the component (f) is not particularly limited, and examples thereof include dicyandiamide.
  • the trimonomer include phenoxyshetyl acrylate, phenoxypolyethylene dalicol acrylate, and phenoxy polypropylene glycol acrylate. Note that a plurality of types may be used in combination. Further, the SP value referred to in the present specification refers to a value calculated by the Fedors method.
  • Such (meth) acrylate monomers are commercially available, for example, A product called light acrylate PO—A (SP value: 10.1) for shetyl acrylate, and a light acrylate P—20 OA (SP value: 10.3) for phenoxypolyethylene glycol acrylate. It is available from Kyoeimori Chemical Co., Ltd.
  • phenoxy polyethylene glycol acrylate is preferably used because it has a low odor, relatively little smoke and odor when irradiated with ultraviolet light, and its effect on workability is large.
  • a copolymer having polystyrene or styrene of the component (2) as a copolymer component is a component which is dispersed or dissolved in the (meth) acrylate monomer of the component (1) which is a main component, Is preferably a thermoplastic resin that increases the transparency of the composition.
  • the melt rate is 0 to 500 minutes (JISK72010 compliant, 200 ° C, 10 kg load).
  • the copolymer having a polymerization component examples include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylenebutylene-styrene block copolymer, and styrene-ethylene.
  • examples thereof include a propylene-styrene block copolymer and a styrene-1,4-butadiene butylene-styrene block copolymer. More preferably, they have a styrene content of 5% by weight or more. In addition, you may use it combining multiple types.
  • composition according to the present invention (1) to (9) will be described.
  • This composition may contain other monomers as long as it does not impair the oil-surface adhesion.It also provides a cross-linking agent such as a polyfunctional monomer or oligomer to impart heat resistance, or imparts low-temperature flexibility.
  • Plasticizers such as phthalic acid esters, other surfactants, oil-absorbing resins, organic-inorganic pigments, stabilizers, etc.
  • a thermal reaction initiator such as an organic peroxide may be included for promoting the curing reaction.
  • the present composition preferably comprises a phosphoric acid group, a sulfonic acid group, a sulfonic acid group, and a sulfonic acid group per 100 parts by weight of the (meth) acrylate monomer having a phenyl group having a molecular weight of 200 or more.
  • the viscosity of the sealing composition is preferably 10,000 to 200,000 mPa's.
  • the viscosity is measured according to J IS K-6830 (Note: Test method for automotive sealing materials).
  • compositions according to the present invention (10) to (11) will be described.
  • the optional components in the present composition are the same as in the above inventions (1) to (9).
  • various curing accelerators may be added to lower the curing temperature by heat.
  • component (a) "100 parts by weight ⁇ if component (c) is present, component (a) + component
  • Component (a) ' is contained in an amount of 20 parts by weight or less (more preferably, 0.1 to 10 parts by weight) based on (a) "+ component (c) 100 parts by weight ⁇ .
  • the preferred composition includes 20 to 200 parts by weight (more preferably 40 to 100 parts by weight) of an epoxy resin and a latent curing agent per 100 parts by weight of two (meth) acrylates, ⁇ 60 parts by weight (more preferably, 4 ⁇
  • the preferred viscosity of the composition is preferably 10,000 to 200,000 mPa's.
  • the composition may contain a monomer having an SP value of less than 9 as long as it does not impair the oil-surface adhesion.
  • a crosslinking agent such as a polyfunctional monomer or oligomer, or a low-temperature flexibility is used.
  • plasticizers such as phthalic acid esters, other surfactants, oil-absorbing resins, organic and inorganic pigments, stabilizers, etc.
  • a thermal reaction initiator such as an organic peroxide may be contained in order to allow a sufficient curing reaction to proceed.
  • hydrophobized silica is not an essential component, but its inclusion is not excluded.
  • the composition preferably contains 5 to 50 parts by weight (more preferably 10 to 50 parts by weight) of component (2) and 0.01 to 100 parts by weight of component (1).
  • the viscosity of the composition is preferably 10,000 to 200,000 mPa's as a sealing agent.
  • the coating agent is preferably from 100 mPa's to 500 OmPa-s.
  • the composition according to the present invention (1) to (9) and (13) to (15) is applied to an adherend according to the same method of use as known sealing agents, and cured by irradiating light with an appropriate light source.
  • the light source is not particularly limited as long as it generates light such as UV, electron beam, infrared light, etc., for example, an ultra-high pressure mercury lamp, a xenon lamp, a mercury xenon lamp, a high pressure mercury lamp, a metal halide lamp. , Medium-pressure mercury lamps, low-pressure mercury lamps, chemical lamps, germicidal lamps, fluorescent lamps for health rays, black lamps, and excimer lasers. One or more of these light sources may be combined.
  • the light source used in the present invention is not particularly limited as long as it generates light such as UV, electron beam, infrared light, etc., for example, an ultra high pressure mercury lamp, a xenon lamp, a mercury xenon lamp, a high pressure mercury lamp, Metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, chemical lamps, germicidal lamps, fluorescent light for health rays Lamps> Black lamps, excimer lasers, etc.
  • a normal heat oven can be used for heating.
  • G photoreaction initiator 3 3 3 3 3 3 translucent, translucent, translucent, translucent, translucent, translucent, translucent, translucent, properties
  • Adhesion evaluation was performed with 1 dragon thickness: ⁇ Peeling not possible, ⁇ Strong adhesion (peelable), ⁇ Slightly weak, X Easy peeling
  • Phenoxyl acrylate (Light acrylate P O_A manufactured by Kyoeisha Chemical)
  • Aerozil R972 (Nippon Aerozil)
  • the following composition was stirred and dispersed by a high-speed stirrer.
  • a transparent to translucent base material was obtained, which was applied to various adherends to a thickness of 2 mm and irradiated with a high-pressure mercury lamp (27 O mW / cm 2 ) for 5 seconds.
  • a high-pressure mercury lamp 27 O mW / cm 2
  • all of the formulations cured within 5 seconds.
  • heating was performed at 180 ° C. for 30 minutes.
  • good adhesion was exhibited without lifting even after heating. Strongly adhered to various adherends (including oil level).
  • Adhesion evaluation (Adhesion evaluation was performed with lmm thickness): ⁇ Peeling not possible, ⁇ Strong adhesion (peeling possible), ⁇ Slightly weak, X Easy peeling, Salt water spray: 35% after spraying 5% salt water Evaluation after leaving for 500 hours
  • Electrocoating condition Voltage 240 V x 10 minutes
  • Epicote 828 manufactured by Japan Epoxy Resin
  • Epicure D CY7 manufactured by Japan Epoxy Resin
  • Aerozil R972 (Nippon Aerozil)
  • a ' phenoxyshetyl acrylate (light acrylate PO-A, manufactured by Kyoeisha Chemical)
  • the energy-curable sealing agents of the present invention (1) to (10) are usually in the same paste form as PVC sealers, they can be easily applied with a sealer gun. In addition, since there is no need for heating and curing can be easily performed in a short time with light, energy costs and work time can be significantly reduced. In addition, it has high adhesion to zinc-plated steel plates and aluminum plates to which press oil and oil-proof oil have adhered, and has an excellent effect that it does not flow down in the oil cleaning process before painting. Low odor during production and construction of products, and has excellent low-temperature flexibility after curing. Furthermore, because it does not contain halogens such as chlorine, it can be easily incinerated and disposed of without polluting the environment.
  • the energy-curable sealing agent of the present invention (11) to (12) is apparently in the form of a paste similar to a vinyl chloride sealer in a normal state, and thus can be easily applied with a sealer gun.
  • the heating step has the effects of improving adhesion to various oily surface materials, increasing hardness, improving low-temperature bending properties, and suppressing the generation of bubbles between the sealing agent and the material after electrodeposition coating.
  • it has high adhesiveness to zinc plated steel and aluminum plates to which press oil, fire prevention oil, etc. adhere, and has an excellent effect of not flowing down in the oil washing process before the painting process.
  • the energy-curable composition of the present invention (13) to (15) can change the product form depending on the composition from a liquid state to a paste state, and has an oil-surface adhesive property.
  • there is no need for heating, and curing can be easily performed with light in a short time, so that energy costs and work time can be significantly reduced.
  • it has high adhesiveness to zinc plated steel and aluminum plates to which press oil, fire prevention oil, etc. are attached, and has an excellent effect of not flowing down in the oil washing process before the painting process.
  • halogen such as chlorine

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Sealing Material Composition (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne une composition de matériau d'étanchéité pouvant durcir par apport d'énergie. L'odeur de cette composition lors de sa production, de son application et de son durcissement a été atténuée. Une fois durcie, cette composition présente une bonne flexibilité à basse température. Cette composition renferme un monomère (méth)acrylate phénylique, qui présente un poids moléculaire supérieur ou égal à 200, ainsi qu'un initiateur de photoréaction.
PCT/JP2001/010529 2000-12-01 2001-12-03 Composition de materiau d'etancheite pouvant durcir par apport d'energie WO2002044299A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2002546649A JP4184788B2 (ja) 2000-12-01 2001-12-03 エネルギー硬化型シーリング剤組成物
US10/433,237 US6818256B2 (en) 2000-12-01 2001-12-03 Energy curable sealant composition
EP01998609A EP1348750A4 (fr) 2000-12-01 2001-12-03 Composition de materiau d'etancheite pouvant durcir par apport d'energie
KR1020037007293A KR100820462B1 (ko) 2000-12-01 2001-12-03 에너지 경화형 실링제 조성물

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JPPCT/JP00/08532 2000-12-01
PCT/JP2000/008532 WO2002044298A1 (fr) 2000-12-01 2000-12-01 Composition a base de materiau d'etancheite photodurcissable

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US10/953,546 Division US20050065228A1 (en) 2000-12-01 2004-09-29 Energy curable sealant composition

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PCT/JP2001/010529 WO2002044299A1 (fr) 2000-12-01 2001-12-03 Composition de materiau d'etancheite pouvant durcir par apport d'energie

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WO2007074519A1 (fr) * 2005-12-27 2007-07-05 Nichiban Company Limited Composition d’agent de scellement pour feuille en acier a surface huileuse
JP2010059355A (ja) * 2008-09-05 2010-03-18 Aisin Chem Co Ltd 紫外線予備硬化型シーリング材
WO2010084913A1 (fr) * 2009-01-22 2010-07-29 日本製紙ケミカル株式会社 Composition de résine durcissable par faisceau d'énergie active

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EP1752494A4 (fr) * 2004-03-31 2009-01-28 Nichiban Kk Composition de résine vulcanisable photoradicale contenant une résine époxy
DE202004008504U1 (de) * 2004-05-28 2004-08-19 Jaband Gmbh Selbstklebeprodukte Korrosionsfeste Versiegelung von Gegenständen aus lackierten Metallblechen, besonders von Fahrzeugkarosserien, durch einen neuen Beschichtungsaufbau
CN101317296A (zh) * 2005-12-01 2008-12-03 加利福尼亚大学董事会 用于离子传导的官能化无机膜
US9486940B2 (en) * 2012-12-18 2016-11-08 Autoliv Asp, Inc. Radiation curable resin systems for composite materials and methods for use thereof
JP6919886B2 (ja) * 2017-05-29 2021-08-18 積水ポリマテック株式会社 封止材組成物および封止材

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Cited By (5)

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WO2007074519A1 (fr) * 2005-12-27 2007-07-05 Nichiban Company Limited Composition d’agent de scellement pour feuille en acier a surface huileuse
JPWO2007074519A1 (ja) * 2005-12-27 2009-06-04 ニチバン株式会社 油面鋼板用シーリング剤組成物
JP2010059355A (ja) * 2008-09-05 2010-03-18 Aisin Chem Co Ltd 紫外線予備硬化型シーリング材
WO2010084913A1 (fr) * 2009-01-22 2010-07-29 日本製紙ケミカル株式会社 Composition de résine durcissable par faisceau d'énergie active
US8748507B2 (en) 2009-01-22 2014-06-10 Nippon Paper Chemicals Co., Ltd. Active energy ray curable resin composition

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KR20030091944A (ko) 2003-12-03
US20040034153A1 (en) 2004-02-19
US20050065228A1 (en) 2005-03-24
JPWO2002044299A1 (ja) 2004-04-02
US6818256B2 (en) 2004-11-16
KR100820462B1 (ko) 2008-04-08
EP1348750A4 (fr) 2009-05-20
JP4184788B2 (ja) 2008-11-19
EP1348750A1 (fr) 2003-10-01

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